Ternary detergent compositions



Patented Dec. 11, 1951 TERNARY DETERGENT COMPOSITIONS Joseph M. Lambert, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N. Y.,. a corporation of Delaware No Drawing. Application March 26, 1947, Serial No. 737,437

3 Claims. (Cl. 252152) This invention relates to an improved germicidal detergent composition comprising a mixture of one of the usual organic anionic active detergents, an organic cationic active germicide and a nonionic organic surface active agent.

A number of organic cation active materials which are surface active and possess germicidal properties have. found quite extensive use as germicides in cleaning operations such as in the food industry, laundering and the like. However, it has been necessary to employ these cation active germicides as a separate rinse or wash, since efforts to combine them with the usual. organic anion active detergents in a single wash have heretofore been unsuccessful., When the organic anion active detergent is combined with a cation active germicide in a single wash, the mixture not only is'- objectionable because of its appearance (inhomogeneity, cloudiness, separation into layers or formation of precipitates), but in addition the detergent power of the mixture is generally noticeably lower than that of the anion active detergent and the germicidal power of the cation active germicidal compound is adversely aifected, such mixtures in practicallyall cases showing noticeably less germicidal activity and at times none at all.

I' have now found that the addition of a small amount of an organic nonionic surface active agent to a mixture of a surface active germicidal cation active material and an organic anionic detergent makes the cation active and anion active compounds compatible, so that not only is the formation of cloudiness or precipitation prevented but in addition the germicidal activity of the mixture is substantially equal to that of the cation active agent alone and the detergency of the mixture is in no way adversely affected and frequently is improved.

Thenonionic surface active agents which I have found, to be effective for incorporation in mixtures of organic anionic detergents and cation active germicides are viscous liquid to waxlike water-soluble surface active inaterials containing a polyether group of thetype in which R." and R are hydrogen or alkyl. The nonionic surface active agents employed are obtained by replacing with a polyglycol ether group an active hydrogen atom of a monomeric organic compound containing at least 6 carbon atoms and an active hydrogen, such as carboxylic acids, amides, amines and organic hydroxy compounds (phenols and alcohols). These watersoluble nonionic surface active agents may be represented by the following general formula:

A(-CHCHO),.H

wherein A represents a residue of a compound selected from the group consisting of a monomeric organic compound containing an' active hydrogen atom (i. e. alcohols and phenols, amides, primary and secondary amines and carboxylic acids) and R and R represent hydrogen or alkyl, and n is an integer greater than three (1. e. the number of alkyleneoxy groups in the polyglycol ether radical is sufficient to impart water-solubility to the product; the exact number of suchgroupswill therefore vary with the particular compound employed but as a general rule at least 1 alkyleneoxy group should be present in the polyglycol ether group for each 2 carbon atoms in the parent compound). Such nonionic surfaceactive agents are well known in the art, having been described, for instance, in U, S. Patent No. 1,970,578 to Schoeller el al. and No. 2,213,477 to Steindorif el al. and may be exemplified by the polyalkylene oxidederivatives (i. e. polyethylene oxide, polypropylene oxide, polybutylene oxide) of water-insoluble higher fatty acids, such as lauric, oleic, palmitic and stearic acid and the like of mixtures thereof, such as the mixtures of fatty acids obtained from animal and vegetable fats and oils or by oxidation of petroleum fractions such as paraflin wax. They may also be exemplified by the polyalkylene oxide derivatives of such water-soluble organic hydroxy compounds as higher aliphatic alcohols (i. e. the alcohols corresponding to the fatty acids specified above or mixtures thereof), oil or phenols, particularly alkylphenols containin at least six alkyi carbon atoms such as'isooctyl, ditertiary butyl, trlisopropyl, nonyl, dodecyl, phenols or naphthols, or of higher alkyl alcohols,

such as benzyl alcohol, cimmamyl alcohol and the like and by the polyalkylene oxide derivatives of water-soluble partial vegetable fatty acid esters of anhydro-sorbitol, such as sorbitan monolaurate,sorbitan monostearate and sorbitan monooleate. They may also be exemplified by the polyalkylene oxide derivatives of such amines as stearyl, lauryl, dicyclohexyl, dibutyl amine and the like. I

The organic cationic active germicidal materials which form one element of the composition of this invention are those cationic agents which are known to possess germicidal properties and include, by way of illustration, germicidal quaternary ammonium compounds, pyridinium compounds and the like. Specific compounds of this type are 8-hydroxy-quinolinium sulfate, cetyl pyridinium chloride, octyl-phenoxy ethoxy ethyl (be yl) dimethyl ammonium chloride, alkyl (8 18 carbon) dimethyl-3.4- dichlor-benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride and the like.

The organic anionic detergents which form another element of the composition of this invention include the usual alkali metal (sodium and potassium) soaps of higher fatty acids of vegetable or animal origin such as hydrogenated cottonseed oil, stearic, lauric, palmitic and similar acids or mixtures thereof of animal or vegetable origin and also the alkali metal soaps of alkyl sulfates and sulfonates, alkylaryl sulfonates and the like, such as sodium cetyl sulfate, hexadecanesulfonic acid sodium salt and diisobutyl-naphthalene-l-sulfonic acid sodium salt.

The relative amounts of organic anionic detergent and cationic surface active germicide which may be employed in the compositions of this invention may be varied through a relatively wide range and as a practical matter, the relative proportions of these two ingredients will depend to a large extent on the specific compounds employed and the specific use for which the composition is intended. Thus, the amount of cationic surface active germicide employed will be such that when the germicidal detergent composition of this invention is added to water for use, the concentration of germicide in the water will be sufficient to give the desired degree of germicidal activity. At the same time the amount of anionic organic detergent employed should be such that when the compound is added to water the detergency of the composition will be satisfactory. When employing the usual alkali metal (sodium and potassium) soaps of higher fatty acids as the organic anionic detergent, the amount of such organic detergent present in the composition of the present invention will generally be in excess of the amount of quaternarytype cationic surface active germicide. However. when employing certain of the newer synthetic organic anionic detergents such as certain alkylaryl sulfonates, satisfactory detergency can frequently be obtained when the cationic surface active germicide is present in excess. Since the relative proportions of the ingredients will vary with the particular agents employed, exact nu-,

merical limits cannot be specified except by way of example. However, those skilled in the art can readily determine the optimum proportions for anyspeciflc combination of components or speciflc application by simple preliminary experiments, and as a practical matter the relative proportions of organic anionic detergent and cationic surface active germicide are generally within the range of 1:4 to 12:1.

gLikewise, the amount of nonionic surface active agent which is incorporated in the composition of this invention may be varied through ayrelatively wide range. The relative compatibility of the organic anionic detergents and cationic germicides is evidenced by the turbidity of dilute aqueous solutions thereof such as would be used in cleaning operations. The turbidity of such solutions is particularly pronounced if there exists a 1:1 stoichiometric ratio between the amounts of anionic and cationic agents in the solution. However, the incorporation of approximately of nonionic surface active agent based on the combined weight of the anionic and cationic agents resulted in the formation of dilute solutions which have very little turbidity and appear almost water-clear. Thus, the mixture of 60 parts by weight of diisobutyl naphthalene-l-sulfonic acid-sodium salt and 40 parts of cetyl pyridinium chloride (total ionic concentration about 0.5 gram per liter) had a turbidity of 64.5 as determined by a Klett colorimeter which reads in 500 density units, while a solution of the same mixture to which had been added 12% (based on weight of ionic agents) of a watersoluble polyethylene oxide derivative of dibutyl phenol had a turbidity determined in the same manner of 3.5 and a solution of 45 parts by weight of diisobutyl naphthalene-l-sulfonic acidsodium salt and 55 parts by weight of cetyl pyridinium chloride had a turbidity of 360, while a similar solution to which had been added 12% (based on weight of ionic agents) of a watersoluble polyethylene oxide derivative of diisobutyl phenol had a turbidity of 5.5. While lesser amounts of nonionic surface active agents are effective for improving the compatibility of anionic organicdetergents and cationic germicides in dilute aqueous solutions of the type employed in cleaning operations, it has been found that compositions containing such minor amounts of nonionic surface agents are not satisfactory in other respects and as illustrated by the examples below, a substantial amount (about 10%) of the nonionic surface active-agent, based on the amount of anionic and cationic agents in the composition should be employed if entirely satisfactory results are to be obtained. Thus, a concentrated solution of these materials such as might be prepared for sale and which contains an amount of nonionic surface active agent of the order of 1% is generally objectionable due to inhomogeneity, cloudiness, separation into layers or the formation of precipitation. However, the appearance of such concentrated solutions can be improved by incorporating a substantial amount of nonionic material therein. Thus, a solution of 20 parts by weight of a potassium fatty acid soap and 2 parts of 8-hydroxy quinolinium sulfate in 78 parts of water was inhomogeneous and separated into a top turbid layer and a clear bottom layer. However, a. mixture of 18 parts of potassium soap, 2 parts of 8-hydroxy quinolinium sulfate and 5 parts of water-soluble polyethylene oxide derivative of dibutyl phenol in 75 parts of water was homogeneous and clear. Thus, in general, the ratio of nonionic agent to the combined weight of the ionic agents is within the range of 1:9 to 1:1 and preferably within the range of 1:9 to 2:3.

It has also been found that substantial amounts (about 10%) of such nonionic agents are necessary if the germicidal activity of the composition is to be satisfactory. Table I below illustrates the eifect of adding various amounts of the water-soluble polyethylene oxide derivative of di-isobutyl phenol .to detergent compositions comprising various mixtures of sodium-N-oleoyl methyl taurate or a conventional sodium soap (Lux flakes), as the anionic organic detergent, with octyl-phenoxy ethoxy ethyl (benzyl) dimethyl ammonium chloride as the cationic germicide. These tests were agar cupplate tests with Staphylococcus aureus, similar tathat described at page 957 of the 8th edition of Text Book of Bacteriology by Zinsser and Bayne-Jones using 25 cc. of melted agar per petri dish and cut cups 1.7 cm. in diameter. Thus, a reading of 1.! cm. means no halos or zero germicidal activity. The parts are by weight.

0.2 gramper' liter.

asvmvs Table I Composition of Detergent Parts Based on Active Rem. of Amountoi Material oermigide Cationic a mas:

Anionic Cationic em. of Halo (gJliter active Nonionic in cm mt Qairmi- Agent material) 5.0 5.0 none 1.7 1.0 6.0 6.0 2.1 0.5 3.0 7.0 none 2.2 1.0 3.0 7.0 1.0 2.5 1.0 3.0 7.0 2.5 2.5 1.0 6.0 4.0 none 2.2 1.0 6.0 4.0 1.0 2.3 1.0 0.0 4.0 2.5 2.4 1.0 none 10 none 2.4 1.0

The effect of addition of nonionic surface-@- tive agents on washing efflciencies of, us mixtures of. organic anionic detergents cationic germicides is illustrated in Table I. below. The parts are by weight.

In Tests A, B and C the anionic detergent employed was a commercial sodium fatty acid toilet soap (Lux flakes) and the cationic germicide employed was octyl-phenoxy ethoxy ethyl (bensyl) dimethyl ammonium chloride. In Tests D, I and l the anionic detergent was a commercial potassium fatty acid soap, the quaternary-type cationic germicide was a-hydroxy quinolinium sulfate, and in all tests in which a nonionic agent was employed the particular agent used was a water-soluble polyethylene oxide derivative of diisobutylphenol. The solutions for these tests were prepared in P. P. M. hard water so that the concentration of germicide in Tests A, B and Cwas1gramperliterandin'1estsD,EandF The tests were made by washing soiled swatches of cloth in a Launder- Ometer for 30' minutes in pint Jars with ml. of detergent solution and 10 stainless steel balls V in diameter. The tests on wool weremade at I". and the tests on cotton at 1''. The swatches had been soiled with a mixture of mineral oil, graphite and cottonseed oil suspended in carbon tetrachloride. The reflectance of the swatches before and after washing was determined with g. Photo-Volt Reflectometer. The results given in Table 11 indicate the washin eilciency in terms of relative detergency (RD) calculated from the reflectance data as follows:

where Rz=reilectance of swatch after washin and Rl=original reflectance of swatch bef re 6 washing. Similar tests carried out with cotton washed with 1.5 grams per liter of the sodium soap employed gave a relative detergency value of 160, while similar tests conducted with wool washed with 3 grams per liter of sodium-N-oleoyl methyl taurate gel gave a relative detergency value of 100.

While the compositions described above represent preferred embodiments of the present invention, it will be understood that variations may be made therein as previously indicated. Thus. while the novel germicidal detergent comfpositions of this invention contain three essen- 1 tial components (an anionic organic detergent, a cationic germicide and a nonionic water-soluble surface active agent containing a polyglycol' ether group) they may 'also contain varying,

amounts of other compoundscustomarily incor-v por ted in detergent compositions such as inor-"-- g ic alkali metal saltssnch as sodium or potas slum phosphates, carbonates, borates and siliv c tes and mutual solvents for water and the ace active agents such as isopropyl alcohol.

I claim: 1. A germicidal detergent composition com prising a mixture of an alkali metal fatty acid soap and a germicidal quaternary ammonium compound in relative proportions of from 1:4 to 12:1. said mixture containing a water-soluble nonionic surface active agent having a polyglycol ethergroup, the ratio of said nonionic agent to the combined weight of said soap and said ouaternary' ammonium compound being,

within the ran e of 1:9 to 1:1.

2. A germicidal deter ent composition comprising a mixture of an alkvl arvl sulfonate deter ent and-a germicidal oua ernarv ammonium compound in r lative proportions of from 1:4 to 12:1, said mixture containing a water-soluble nnnionic surface active a ent having a polyglycol ether group, the ratio of said nonionic agent to the combined wei ht of said alkvl aryl sulfonate and said ou ternarv ammonium compound being within the range of 1:9 to 1:1.

3. A germicidal d tergent composition comprising a mixture of an or anic anionic detergent and a germicidal euaternarv ammonium compound in relative proportions of from 1:4 to 12:1, said mixture containing a water-soluble nonionic surface active a ent having a polyglycoi ether group. the ratio of said nonionic a ent to the combined weight of said anionic detergent and said quaternary ammonium compound being within the r n e of 1:9 to 121.

JOSEPH M. LAMBERT.

REFERENCES CITED The following references are. of record in the tile of this patent:

UNITED STATES PATENTS o'rmm nnrnnsncss Goldsmith, reprint from Chemical Industries entitled "Non-Ionic Surface Active Agents.

Young and Coons, Surface Active Agents (1945), pp. 110, 111. 

3. A GERMICIDAL DETERGENT COMPOSITION COMPRISING A MIXTURE OF AN ORGANIC ANIONIC DETERGENT AND A GERMICIDAL QUATERNARY AMMONIUM COMPOUND IN RELATIVE PROPORTIONS OF FROM 1:4 TO 12:1, SAID MIXTURE CONTANING A WATER-SOLUBLE NONIONIC SURFACE ACTIVE AGENT HAVING A POLYGLYCOL ETHER GROUP, THE RATIO OF SAID NONIONIC AGENT TO THE COMBINED WEIGHT OF SAID ANIONIC DETERGENT AND SAID QUANTERNARY AMMONIUM COMPOUND BEING WITHIN THE RANGE OF 1:9 TO 1:1. 